EP0543814B1 - Verfahren zur herstellung eines wärmedämmenden geschäumten plastikmaterials und bei diesem verfahren verwendetes treibmittel - Google Patents

Verfahren zur herstellung eines wärmedämmenden geschäumten plastikmaterials und bei diesem verfahren verwendetes treibmittel Download PDF

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Publication number
EP0543814B1
EP0543814B1 EP91902261A EP91902261A EP0543814B1 EP 0543814 B1 EP0543814 B1 EP 0543814B1 EP 91902261 A EP91902261 A EP 91902261A EP 91902261 A EP91902261 A EP 91902261A EP 0543814 B1 EP0543814 B1 EP 0543814B1
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Prior art keywords
blowing agent
plastics
xenon
krypton
plastic
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EP91902261A
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English (en)
French (fr)
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EP0543814A1 (de
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Torben Hove Jensen
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Edulan AS
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Edulan AS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/05—Use of one or more blowing agents together
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/91—Plural blowing agents for producing nonpolyurethane cellular products

Definitions

  • the present invention relates to a method for the manufacture of a heat insulating foamed plastic material by foaming of a plastic material or plastic precursor material by means of a blowing agent, a blowing agent to be used by the method, the use of a mixture comprising krypton and xenon as the blowing agent and a heat insulating foamed material prepared according to the method.
  • CFC substances chlorofluorocarbons
  • CFC 11 trichlorofluoromethane
  • HCFC substances which in addition to halogen atom(s) contain at least one hydrogen atom
  • Said substances distinguish themselves from the traditional CFC substances in that they are less stable and therefore only a smaller quantity is expected to reach the upper atmosphere.
  • the decomposition products of said materials may however be expected to cause other environmental problems, for instance hydrochloric acid rain and hydrofluorid acid rain.
  • the preparation of HCFC substances will be substantially more costly than the preparation of CFC substances.
  • the heat conduction taking place through the gas present in the cavity of the cells contributes considerably to the total thermal conductivity of the insulating material, said contribution conventionally comprising about half of the heat conduction in the case where the cells are filled with CFC 11. Therefore, when preparing a foamed plastic material with a good heat insulating capacity, it is decisive that the gas present in the cells per se have a low thermal conductivity.
  • This object is obtained by a method for the preparation of a heat insulating foamed plastic material by foaming a plastic material or a plastic precursor material by means of a blowing agent, said method being characterised by using a mixture of krypton and xenon, optionally together with one or more other CFC-free blowing agents as the blowing agent.
  • Krypton and xenon might thus be candidates to replace CFC gases.
  • a person skilled in the art will find that the market price for krypton and xenon, respectively is per se prohibitive for the use thereof on a large technical scale.
  • a fraction recovered from atmospheric air with a high content of krypton and xenon may be used directly, for instance the highly concentrated Kr-Xe crudes, described in Kirk-Othmer "Encyclopedia of Chemical Technology", 3rd Edition, 1982, Volume 12, page 267.
  • the thermal conductivity of a mixture of more gases will usually be lower than the thermal conductivity calculated by interpolation of the thermal conductivity of the individual constituents. This is the reason why the mixture of xenon and krypton used does not need any particularly high degree of purity and this is also the reason why the mixture may advantageously be used in combination with conventional environmentally acceptable blowing agents and still obtain a substantially improved low thermal conductivity compared to said conventional environmentally acceptable blowing agents.
  • the present invention also provides a blowing agent to be used by the above method, said blowing agent being characterised by containing a mixture of xenon and krypton.
  • the invention also relates to a heat insulating foamed plastic material comprising gas filled cells confined in a plastic matrix prepared by the method according to the invention.
  • the foamed plastic material may have cells filled with KX-gas alone or with KX-gas in a mixture with other blowing agents. Because of the low thermal conductivity, it will often be an advantage to use KX-gas alone but as the ⁇ -value of a mixture of more gases is usually lower than the thermal conductivity calculated by interpolation, substantial advantages are still obtained by using KX-gases admixed with other blowing agents. KX-gas is thereby saved.
  • the blowing agent used together with KX-gas may be any known blowing agent and may advantageously be selected among carbondioxide, carbonmonoxide, nitrogen, atmospheric air, argon, volatile hydrocarbons or mixtures thereof.
  • the plastic matrix forming part of the foamed plastic material may be of any kind of material suitable as plastic foam.
  • thermoset examples include polyurethane, polyisocyanurate, unsaturated polyester, including vinyl ester, allyl plastics, phenolic plastics and the like such as types of plastics prepared by condensing formaldehyde with monovalent or polyvalent phenoles or furanoles, amino plastics, including urea-formaldehyde plastics and melamine-formaldehyde plastics, amide plastics, imide plastics, epoxide plastics as well as vulcanized elastomers, for instance natural rubber and ethylene-propylene-terpolymer rubber.
  • thermoset examples include polyurethane, polyisocyanurate, unsaturated polyester, including vinyl ester, allyl plastics, phenolic plastics and the like such as types of plastics prepared by condensing formaldehyde with monovalent or polyvalent phenoles or furanoles, amino plastics, including urea-formaldehyde plastics and melamine-formaldehy
  • thermoplastics examples include vinyl plastics, such as polystyrene, polyvinyl chloride and acrylic ester plastics, polyolefins, such as polyethylene and polypropylene, including polyolefins which are crosslinked in connection with or after the foaming, amide plastics, imide plastics, polyurethane, ester plastics, polycarbonate, acetal plastics, polyphenylene oxide, various copolymers such as for instance ABS (acrylate -butadien-styrene) and thermoplastic elastomers.
  • vinyl plastics such as polystyrene, polyvinyl chloride and acrylic ester plastics
  • polyolefins such as polyethylene and polypropylene, including polyolefins which are crosslinked in connection with or after the foaming
  • amide plastics imide plastics
  • polyurethane polyurethane
  • ester plastics polycarbonate
  • acetal plastics polyphenylene oxide
  • various copolymers such as for instance
  • the plastic matrix used is polyurethane plastics.
  • Said material is particularly suitable for use when manufacturing heat insulating foamed materials, as polyurethane provides particularly favourable opportunities for tailoring a product by varying the quantity and type of plastic starting materials used.
  • Krypton and xenon have a thermal conductivity of 9.5 and 5.5 mW/m°K, respectively, which is of the same order as for CFC 11 where it is 8 mW/m°K. It will thus be possible to obtain a heat insulating material with substantially the same good heat insulating properties as when using CFC substances.
  • the foaming may be carried out by means of prior art known per se for foaming using only gas as blowing agent or gas in a combination with other conventional blowing agents.
  • the apparatus used for the foaming may be any known apparatus for use in such foaming processes.
  • a mixture of krypton and xenon or a mixture of krypton and xenon with one or more known blowing agents for instance H2O/CO2, HCOOH/CO, argon, nitrogen, oxygen, atmospheric air, volatile hydrocarbons or similar known blowing agents, is used as the blowing agent.
  • blowing agent for instance H2O/CO2, HCOOH/CO, argon, nitrogen, oxygen, atmospheric air, volatile hydrocarbons or similar known blowing agents.
  • KX or "KX-gas” designate a mixture of krypton and xenon.
  • KX or, if the plastic material used is polyurethane, a combination of KX and H2O/CO2 is preferably used.
  • the total blowing agent comprises liquid or solid substances
  • said substances are added to the plastic material in a conventional manner, that is usually before the addition of the gaseous components of the blowing agent.
  • H2O/CO2 as a portion of the blowing agent used for foaming polyurethane
  • the water is thus added to the polyol component beforehand.
  • formic acid may be added to the polyol component whereby carbonmonoxide is developed by the reaction with the isocyanate component.
  • the gaseous component(s) of the blowing agent may be added to the plastic raw material by dissolving or dispersing.
  • gaseous blowing agents may be added either to one of the components or both. Dispersion of a gaseous blowing agent may for instance take place by beating or by adding the blowing agent under pressure through a porous material or a combination of both.
  • blowing agent both by dissolution and by dispersion, must take place under a pressure exceeding the pressure under which the pouring is to take place.
  • the raw materials must be kept at a suitably high pressure, thereby preventing the blowing agent from being released prematurely.
  • the additon of the blowing agent may advantageously be carried out in a mixing device in connection with the pouring per se.
  • blowing agent takes place at suitable temperatures depending on the material and equipment used, for instance at a temperature between 10°C and 70°C.
  • the amount of gaseous blowing agent used is determined by the required properties of the final heat insulating foam, such as the bulk density of the foam, and by the amount of possibly supplementary blowing agents, for instance H2O/CO2.
  • the amount of gasous blowing agent to be used when preparing the heat insulating foamed plastic material according to the invention can easily be calculated by a person skilled in the art.
  • When preparing foam having a density of 50 g/l using only KX-gas as blowing agent about 19 parts by volume KX-gas are used for each part by volume plastic raw material.
  • the above volume is calculated at a pressure of 1 bar. Using such ratio of volume a foamed material is obtained where about 95% of the volume is made up of cells containing blowing agents.
  • the above computations are, however, theoretical, as in practice an adjustment must be made for a loss of blowing agent and the final pressure in the cells which may deviate from 1 bar. Such adjustments must be determined on the basis of simple tests carried out in connection with the production in question
  • the final foam When using dispersion, it is aimed at obtaining as small bubbles as possible as usually as small cells as possible are desirable in the final foam. To obtain a good thermal conductivity the final foam should have a average cell diameter below 1.5 mm, preferably below 0.5 mm. On the basis of this requirement, the permisible bubble size may be calculated on the basis of such parameters as the dispersion pressure and the pouring pressure used.
  • the pouring may for instance be carried out in the manner usually known for foaming.
  • the dissolved or dispersed blowing agent causes foaming, as dissolved blowing agent is released and dispersed bubbles are expanding.
  • the heat formed by the reaction between the plastic materials just mixed furthermore accelerates the release and the expansion of the bubbles and thereby supports the formation of foam.
  • a chemically reacting blowing agent is used supplementarily together with the gasous blowing agent, the development of gas resulting from the chemical reaction takes place simultaneously with or a little after the physically determined foaming.
  • Water admixed with the polyol component of polyurethane may be mentioned as an example of a chemically reacting blowing agent. During the reaction, the water added reacts with the isocyanate component while developing CO2 which contributes to the foaming.
  • any type of plastic material suitable for the preparation of foamed plastics may be used as the plastic material forming part of the heat insulating foamed plastic material according to the invention.
  • the manufacture of a material of plastics is usually carried out through a phase in which the material is sufficiently plastic to be shaped or moulded by means of pouring, injection moulding, compression moulding.
  • Conventional plastic materials are usually divided into the two main groups thermoplastics and thermoset.
  • Thermoplastics are characterised in that a plastic conditon is obtainable by heating the material. After the moulding. the material has a substantially unchanged chemical structure, whereby it is possible to melt down the materials.
  • Thermoset is characterised in that the moulding involves a chemical reaction usually implying a crosslinking of the molecular chains in such a manner that the product is not thermoplastic.
  • the raw material for the preparation of thermoset may be present as one or more components which in the condition supplied may be liquid or solid.
  • the setting reaction may be started thermically or chemically. Examples of such setting reactions are described below.
  • Polyurethane is prepared by reacting a polyol with an isocyanate whereby among other things urethane bonds are formed between the polyol component and the isocyanate component.
  • the raw material components are supplied in a liquid state and have a good storability, also after the addition of possible auxiliary agents.
  • the two components are usually mixed at room temperature or at a sligtly elevated temperature.
  • the chain length and the degree of crosslinking of the reaction product depend on the number of functional groups of the polyol component and the isocyanate component and of the catalysts used, as well as of temperature and other conditions during the reaction.
  • the mechanical properties of the polyurethane material formed may be controlled within wide limits and it is thus well known to persons skilled in the art how the required foaming conditions and desired properties of the final foamed product are secured through the selection of starting components and reaction conditions.
  • Polyurethane is advantageous in that it is a relatively inexpensive material.
  • a varity of polyurethane is polyisocyanurate whose chemical structure is characterised by heterocyclic groups. Polyisocyanurate is suitable for foaming and posseses particularly good fireproof properties.
  • Polyester plastics may be prepared by reacting unsaturated polyester resins and compounds copolymerizable therewith. Examples include crosslinking of unsaturated oligo esters dissolved in styrene as the copolymerizable material. Said reaction may be carried out by means of a free-radical-reaction, for instance by adding organic peroxides which open double bonds in the ester chains and in styrene. Traditionally such liquid, cold-setting polyesters are used for the preparation of glass fibre reinforced constructions. The material is, however, also suitable for foaming. The range of possible variations of the properties is however far narrower than for polyurethane. Polyesters are also an inexpensive material.
  • Phenolic plastics may be prepared by condensation of phenol with formaldehyde.
  • plastic raw material a not fully condensated intermediary product is used, the properties of which among other things depend on whether an excess of phenol or of formaldehyde has been used.
  • the type of phenol plastics where the raw material is liquid is suitable for foaming.
  • foamed plastics from phenol plastics by direct reaction between phenol and formaldehyde during the foaming.
  • the possible scope of possiblities is essentially narrower than is the case with polyurethane. However, the price is low and the fireproof properties are extremely good, as phenol plastics is self-extinguishing.
  • Resorcinol, melamin and urea may also be condensed with formaldehyde to form intermediary products with corresponding possible applications as phenol plastic raw materials.
  • the prices of such materials are, however, higher than those of phenol plastics.
  • blowing agents may be used for the manufacture of foamed plastics.
  • the effect of a blowing agent is due to the occurence at a suitable time during the processing of the plastic raw material of such physical and/or chemical conditions in the plastic mass that a release of gas takes place in a great number of points evenly distributed over the mass.
  • Said gas release which provides the material with a cell structure may be based on purely physical conditions or on a chemical reaction.
  • liquid or gaseous blowing agents are used which are introduced into the plastic mass or one or more of the plastic raw materials beforehand.
  • the physical conditions causing the release of gas and thereby the foaming is usually a rise in temperature (usually as reaction heat) and/or a drop in pressure but may also be changed solubility conditions because of chemical reactions or the gas release may be caused by the introduction of particle material acting as graft.
  • the KX-gases are included in the blowing agents whose effect is purely physical.
  • blowing agents may affect the properties of the solid plastic material by possibly acting as softener. Such effect is usually unfavourable and undesirable. As the KX-gases are chemically inactive, they do not cause such unfavourable effects. The mechanical properties and the dimensions of a foamed material formed may furthermore change over time as the blowing agent evaporates, unless this if prevented by sealing the surface.
  • a pre-foaming technique may be used, where CFC 11 in combination with a blowing agent having a low boiling point, such as CFC 12, nitrogen or CO2, dissolved in the raw materials under pressure is traditionally used.
  • the low-boiling blowing agent forms a pre-foam immediately when the raw material mixture leaves the mixing head, whereupon the reaction heat gradually releases the portion of the blowing agent having a higher boiling point thereby filling the mould or the volume required.
  • KX-gases may also be used in such pre-foaming technique, possibly in combination with other environmentally acceptable blowing agents.
  • foamed plastics for heat insulating purposes may take place by means of conventional equipment.
  • the equipment used is of course determined by the type of plastic in question.
  • Polyurethane foam is either manufactured as block foam or by pouring the cavities which it is desired to insulate.
  • block foaming which may optionally be arranged as a continuous process, the raw material mixture is introduced by means of a lance (i.e. a lance or spear shaped pole with a nozzle) which is moved according to a fixed pattern.
  • a lance i.e. a lance or spear shaped pole with a nozzle
  • large foamed blocks are manufactured which are cut out to plates, for instance for use when heat insulating buildings.
  • Direct foaming to fill out cavities is among other things used when manufacturing refrigerators and pipes for district heating.
  • the mixture of the raw materials prior to the pouring takes place in mixing devices according to well known principles.
  • the admixture of a gasous blowing agent for pre-foaming typically takes place by agitating the raw material while the blowing agent is introduced in the bottom of the container at an overpressure of a few bar.
  • thermoplastics suitable for foaming include polystyrene, polyvinylchloride and polyolefines.
  • polystyrene foam is the most important thermoplastic foam used for heat insulating. More methods are known for the manufacture of polystyrene foam. The two most commonly known methods are 1) expansion of pre-expanded granulate in a mould cavity, and 2) foaming in connection with extrusion.
  • the pre-expanded granulate used for method 1) is manufactured on the basis of polystyrene grains containing a blowing agent rendering possible foaming, that is pre-expansion, of the grain by heating.
  • a known blowing agent is pentan.
  • the pre-expanded granulate may be filled in a mould to which steam is led, said steam causing som further expansion and welding of the granulate.
  • the polystyrene material must contain either a chemical blowing agent which is split at a temperature below the extrusion temperature or a physical blowing agent dissolved under pressure in the melted polystyrene in the extruder. As the melt leaves the extruder, the drop in pressure causes foaming. It appears that in both the foaming methods for polystyrene and corresponding thermoplastics described it is possible in accordance with the present invention wholly or partially to use KX-gas as blowing agent.
  • the conductivity of a foamed plastic material is composed of three contributions to heat conduction:
  • ⁇ for a mixture of two gases does not correspond to the one found by means of a linear interpolation.
  • the resulting ⁇ -value is thus determined mostly by the one of the gases having the lowest thermal conductivity. This may be utilized in practice if for environmental or economic reasons it is desired to save on a blowing agent with low ⁇ -value. It is this well known that polyurethane foam with CFC 11 still has an acceptably low ⁇ -value, even with a considerable CO2 content. CO2 may also be combined with KX-gases.
  • KX-gas used it is not necessary for the KX-gas used to have a particularly high degree of purity. Therefore it is possible to manufacture KX-gas at a technically acceptable price on the basis of atmospheric air, although the content in atmospheric air is only 10.8 x 10 ⁇ 5 volume% krypton and 0.8 x 10 ⁇ 5 volume% xenon.
  • the heat insulating material for instance can be used for insulation of pipes for district heating, it may be assumed that a large demand for KX-gases will arise which in its turn will be an incentive for developing more inexpensive methods for isolating KX-gases from the atmospheric air.
  • xenon is the one of the KX-gases having the lowest thermal conductivity
  • KX-gas mixtures having a higher content of xenon than the one corresponding to a volume ratio between krypton and xenon of 27:2, corresponding to the ratio of atmospheric air, may advantageously be used.
  • other sources especially more xenon containing sources than atmospheric air may become relevant.
  • the fraction of closed cells in the foam is decisive to the heat insulating benefit of a blowing agent.
  • polyurethane foam excluding integral foam
  • the other cells are connected to the surface of the foam and if the surface is not sealed, said cells provide access to atmospheric air having a high ⁇ -value.
  • the present Example illustrates the manufacture of polyurethane foam on a laboratory scale by foaming with KX-gas.
  • the KX-gas used contains krypton and xenon in a volume ratio of about 27:2.
  • a polyol mixture having the following composition is prepared: CARADOL TM 555-1 100 g DIME TM 6 1 g TEGOSTAB TM B8404 1 g Waterfree glycerol 3 g
  • CARADOL TM is a polyol component available from Shell.
  • DIME TM 6 is a catalyst in the form of N,N-dimethylcyclohexylamine, available from Shell.
  • TEGOSTAB is a trademark not registered in Denmark for a foam control agent available from Th. Goldschmidt AG, Essen.
  • a polyol mixture having the following composition is prepared: CARADOL TM 555-1 100 g DIME TM 6 1 g TEGOSTAB B8404 1 g Water 1 g
  • Example 2 200 g of the above mixture is treated in a calorimeter bomb to absorb KX-gas in the same manner as in Example 1.
  • 350 g isocyanate component (CARADATE TM 30) is treated in the same way.
  • the components are quickly mixed and 500 g of the mixture is poured into a 4 litre box-shaped aluminum mould which is immediately closed with a lid. After foaming and cooling the material is taken out of the mould and the material is analysed in the same manner as described in Example 1.
  • the present Example illustrates free foaming of polyurethane using the KX-gas used in Example 1 as blowing agent in a laboratory test.
  • Example 2 The test is carried out in the same manner as in Example 1 apart from 100 g of the mixture of components being poured into a 1 litre open plastic cup for free foaming. In the test, cream time, rising time and non-adhesive time are determined.
  • the present Example illustrated the manufacture of polyurethane foam during free foaming with the KX-gas used in Example 1 in combination with H2O/CO2 on a laboratory scale.
  • the embodiment of the invention best known at present is the manufacture of heat insulating foamed plastic material in the form of foamed polyurethane.

Claims (8)

  1. Verfahren zur Herstellung eines wärmedämmenden geschäumten Kunststoffmaterials durch Schäumen eines Kunststoffmaterials oder Kunststoffvorläufermaterials mittels eines Blasmittels, dadurch gekennzeichnet, daß eine Mischung von Krypton und Xenon, gegebenenfalls zusammen mit einem oder mehreren anderen CFC-freien Blasmitteln als Blasmittel verwendet wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß Krypton und Xenon in Kombination mit einem herkömmlichen Blasmittel als Blasmittel verwendet wird.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Kunststoffmaterial oder Kunststoffvorläufermaterial ein Kunststoffprodukt ist ausgewählt aus Polyurethan, Polyisocyanurat, ungesättigtem Polyester, Allylkunststoffen, Imidkunststoffen, Epoxidkunststoffen, vulkanisierten Elastomeren, Vinylkunststoffen, Polyolefinen, Esterkunststoffen, Polycarbonat, Acetalkunststoffen, Polyphenylenoxid und ABS-Kunststoffen.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das Kunststoffvorläufermaterial ein Vorläufermaerial für Polyurethankunststoffe ist.
  5. Blasmittel, das im Verfahren nach Anspruch 1 einsetzbar ist, dadurch gekennzeichnet, daß es eine Mischung von Krypton und Xenon enthält.
  6. Blasmittel nach Anspruch 5, dadurch gekennzeichnet, daß die Mischung von Krypton und Xenon ungereinigt ist.
  7. Verwendung einer Mischung von Krypton und Xenon als Blasmittel.
  8. Wärmedämmendes geschäumtes Kunststoffmaterial, das gasgefüllte Zellen, eingeschlossen in einer Kunststoffmatrix aufweist, die nach dem Verfahren nach Anspruch 1 hergestellt ist.
EP91902261A 1989-12-29 1990-12-28 Verfahren zur herstellung eines wärmedämmenden geschäumten plastikmaterials und bei diesem verfahren verwendetes treibmittel Expired - Lifetime EP0543814B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK6744/89 1989-12-29
DK674489A DK674489D0 (da) 1989-12-29 1989-12-29 Varmeisolerende skumplastmateriale, fremgangsmaade til fremstilling deraf samt opskumningsmiddel til anvendelse ved fremgangsmaaden
PCT/DK1990/000347 WO1991009901A1 (en) 1989-12-29 1990-12-28 Method for the manufacture of a heat insulating foamed plastic material and blowing agent to be used by the method

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Publication Number Publication Date
EP0543814A1 EP0543814A1 (de) 1993-06-02
EP0543814B1 true EP0543814B1 (de) 1994-10-12

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US (1) US5266251A (de)
EP (1) EP0543814B1 (de)
AT (1) ATE112789T1 (de)
AU (1) AU643973B2 (de)
CA (1) CA2071836A1 (de)
DE (1) DE69013365T2 (de)
DK (2) DK674489D0 (de)
FI (1) FI922950A0 (de)
HU (1) HUT63643A (de)
NO (1) NO922396D0 (de)
RU (1) RU2044745C1 (de)
WO (1) WO1991009901A1 (de)

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WO2019140496A1 (ru) * 2018-01-18 2019-07-25 Николай Марков АНАТАСОВ Технология композитных интегральных изоляционных конструкций для строительства
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RU2044745C1 (ru) 1995-09-27
HU9202168D0 (en) 1992-10-28
FI922950A (fi) 1992-06-25
CA2071836A1 (en) 1991-06-30
US5266251A (en) 1993-11-30
WO1991009901A1 (en) 1991-07-11
AU7064091A (en) 1991-07-24
FI922950A0 (fi) 1992-06-25
DE69013365T2 (de) 1995-02-23
DK674489D0 (da) 1989-12-29
EP0543814A1 (de) 1993-06-02
AU643973B2 (en) 1993-12-02
NO922396L (no) 1992-06-18
ATE112789T1 (de) 1994-10-15
DE69013365D1 (de) 1994-11-17
NO922396D0 (no) 1992-06-18
DK0543814T3 (da) 1995-04-18
HUT63643A (en) 1993-09-28

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